Process for the production of basic modified polyamides

ABSTRACT

This invention relates to the production of basic modified polyamides produced by the polycondensation of lactams or omega -aminocarboxylic acids with 0.1 to 5 mol of triamines of the formula H2N - (CH2)n - NH - (CH2)n - NH2 where n equals 2 to 6 PER 100 MOL OF LACTAM AND 2 EQUIVALENTS OF CARBOXYL GROUPS IN THE FORM OF DICARBOXYLIC ACIDS AND MONOCARBOXYLIC ACIDS PER MOL OF TRIAMINE, USING A MOLAR RATIO OF MONOCARBOXYLIC ACIDS TO DICARBOXYLIC ACIDS OF BETWEEN 10 : 1 AND 1 : 20, WHICH POLYAMIDES ARE DYED WITH REACTIVE DYES.

SSTaTs PTeT Thoma efi all, July 1975 [54] PRGCESS TGR THE PRUDTJCTTGN QT3,465,060 9/1969 Oldham 260/78 L X BASH: MQDHFHED PULYAMIDES 3,549,60112/1970 Powell 260/78 TF 3,640,841 2/1972 Winslow et a1. 260/78 TF Xlnventors: Wilhelm T119919, g Neukirchen; 3,687,904 8/1972 Middleton260/78 TF x Dietrich Hildebrand, Odenthal; Wollfi-Diefter Last; HeinrichRinlke, both of Leverkusen, all of Germany Primary Examiner 44101116Phynes Attorney, Agent, or Firm-lPlumley & Tyner [73] Assignee: BayerAlktiengeseTlschaft,

LeverlcusenBayerwerk, Germany [22] Filed: .llully 6, 11973 [57] ABSTRACT[21] Appl' 377mm) This invention relates to the production of basicmodified polyamides produced by the polycondensation of [30] FmefiApplicaltiun Priority D m lactams or w-aminocarboxylic acids with 0.1 to5 mol July 8, 1972 Germany 2233768 of mammes Ofthe formula July 8, 1972Germany 2233703 z (Cll'l NH (CT-l NH where n equals 2 to 6 [52] (CH260M713 L; 260/37 N; 260/37 NP; per 100 mol of lactam and 2 equivalentsof carboxyl 260/78 A; 260/78 TlF; 264/176; 264/210 groups in the form ofdicarboxylic acids and monocar- [5 y i acids p o of a e, u g a m ar rato [58] lFnelld M Search 260/78 L, 78 TP of monocarboxylic acids todicarboxylic acids of tween 10 1 and 1 20, which polyamides are dyed[56] References Cited with reactive dyes UNITED STATES PATENTS 3,320,2155/1967 Conte et a1 260/78 L 8 TClaims, 11 Drawing Figure PKMDUESS NORTHE EPRQDUCTHUN @l BASH: M ODEllFllED PULYAMHDES This invention relatesto a process for the production of basic modified polyamides and threadsand fibres made of such polyamides. These threads and fibres can be dyedwith reactive dyes to produce deep colours which are fast to light,perspiration, water, boiling washes and detergents.

it is known that polyamides and, in particular polyamides produced fromlactams, can be dyed with reactive dyes. Compared with dispersion dyesand acid dyes which are nowadays mainly used for dyeing polyamides,reactive dyes have numerous remarkable advantages which can beattributed to the reaction between the reactive dye groups and thefunctional groups of the polyamides to form covalent chemical bonds. Oneparticular advantage, for example, is the astonishing improvement in thefastness of the colours obtained by dyeing polyamides with reactivedyes. In their fastness to water, perspiration and abrasion, reactivedyes are distinctly superior to conventional dyes.

The capacity of polyamide fibres to absorb reactive dyes is, however,limited and hence the depth of colour which can be obtained on normalstandard polyamides is correspondingly limited and dyeings which havethe high fastness to perspiration, water and boiling washescharacteristic of reactive dyes cannot be obtained with more than 2% ofreactive dye in the polyamide. The quantity of reactive dye which can befixed by the fibres is limited by the number of functional end groups inthe polyamide and is generally not more than 2%. An additional quantityof dye may occasionally be present in the form of a salt which caneasily be removed by washing with alkaline soaps.

it is also known that basic modified polyamides which contain tertiaryamino groups in the chain have a higher dye absorption capacity for aciddyes and anionic reactive dyes than polyamides which contain only aminoend groups.

if the dye content is more than the average of 2%, however, the fastnessto perspiration, water and washing of reactive dyeings on suchpolyamides which are modified with tertiary amino groups is no betterthan on polyamides in which the only basic groups are amino end groupsbecause the tertiary amino groups do not react with the reactive groupof the reactive dye and therefore it is only the absorption capacity forthe dye molecules which are bound as salts which is increased. Thefastness to perspiration, water and washing of the reactive dyeings onpolyamides which are basic modified with tertiary amino groups istherefore determined solely by the number of amino end groups present.

it is also known that the dye absorption capacity of polyamides can beimproved by increasing the number of amino end groups in the polyamides.This can be achieved, for example, by adding free amines to thepolyamide-forming starting materials before polycondensation is carriedout. The amines used for this purpose may be aliphatic monoor polyaminesor heterocyclic amines. Polyamides with an increased number offunctional groups (amino end groups) produced by this method are,however, difficult to spin. if it is attempted to obtain a substantialimprovement in the dye absorption by adding a correspondingly largerquantity of amine, then the polyamide mass tends to form drops whenattempts are made to spin it, in other words spinning is no longerpossible.

According to one known process (Belgian Pat. Specification No. 693,000),an appropriate quantity of an aliphatic dicarboxylic acid such as adipicacid or glutaric acid may be added to the polyamide before condensationin addition to the polyamine, the quantity used being 0.3 to 1.1 mol ofdicarboxylic acid per mol of polyamine. This method, however, has thedisadvantage that cross-linked structures are likely to be formed by thereaction of the dicarboxylic acid with all three amino groups of thepolyamine. This is found to be a disadvantage when attempts aresubsequently made to produce threads, fibres or films from the resultingpolyamides. This formation of cross-linked structures is facilitated bythe fact that if polyamines contain less than three carbon atoms betweenthe primary and secondary amino groups then there is little differencebetween the reactivity of the different amino groups and it is only aquestion of time before cross-linking takes place and the polyaminecreases to be spinnable. This method cannot therefore in practice beused for the production of high molecular weight, linear polyamides forspinning.

it is also known to use aliphatic or aromatic monocarboxylic acids suchas acetic acid or benzoic acid as polycondensation regulating agents.Furthermore, in British Pat. Specification No. 1,065,363, it has beenproposed to use dicarboxylic acids and monocarboxylic acids in additionto polyamines. It could be shown that special properties of thepolyamides could be influenced in the desired manner by using suitablequantities of dicarboxylic acid and monocarboxylic acid. Although thepolyamides obtained by this method are suitable for use as hardeners forepoxy resins, it is not possible to modify these compounds with thegiven proportions of monocarboxylic acid, dicarboxylic acid and lactamin such a way as to obtain high molecular weight, linear polyamideswhich could be spun; nor was this to be expected.

it has now been found that basic modified polyamides and productsproduced from them such as threads, films or fibres which can be dyedwith reactive dyes to produce lightfast dyeings which are fast toperspiration, water and boiling washes, even if the products are dyed todeep colour tones, can be obtained by the polycondensation ofpolyamide-forming starting materials, in particular lactams, in thepresence of aliphatic triamines of the formula H N-(CH ),,NH(CH ),,NHwhere n 2 to 6, dicarboxylic acids and monocarboxylic acids if thereactants are used in proportions corresponding to 0.1 to 5.0 mol andpreferably 1.0 to 2.0 mol of an aliphatic triamine of the above formulaper mol of polycondensable lactam and two equivalents of carboxyl groupsin the form of dicarboxylic acids and monocarboxylic acids per mol oftriamine and the molar ratio of monocarboxylic acids to dicarboxylicacids is between 10:1 and 1:20, preferably between 3:1 and 1:3.

This invention therefore relates to a process for the production of abasic modified polyamide by the polycondensation of a lactam or anw-aminocarboxylic acid in the presence of a triamine of the formulall-ll l l(CH ),,N1-l-(CH ),,Nl-l wherein n equals 2 to 6, a dicarboxylicacid and a monocarboxylic acid, which comprises adding to the reactivemixture 0.1 to 5.0 mol of the aliphatic triamine per 100 mol ofpolyspermidine, l diaminodihexylamine are suitable aliphatic triaminesfor the process. The amines may be used as mixtures condensable lactamand 2 equivalents of carboxyl groups in the form of dicarboxylic acidsand monocarboxylic acids per'molof triamine and the molar ratio ofsaidmonocarboxylic acids to-said dicarboxylic acids being between l and.l :..20.

'Theprocess according to the invention for producing the basic modifiedpolyamides'which can be dyed with reactive dyes to-'produce lightfastdyeings which are fast to perspiration, water andboiling detergents evenif the dyeings are in deep colour tones is carried out by theiusualmethods used for producing the corresponding unmodified polyamides,which consist of adding the modifying agents to the. usualpolyamide-forming lactams or w-aminocarboxylic acidsfil he process isgenerally carried out by keeping the mixture of components in the givenproportionsin an autoclave at temperatures above 2009C and preferably at250 to 275C for 4 to 10 hours with exclusion of oxygen to effectpolycondensation'and then processing the resultingbasic modifiedpolyamide melts to produce shaped structures such as threads,.films orfibres. The production of basic modified polyamides-in accordance withthe invention is not affected by the addition of pigments, stabilizers,brightening agents and similar substances but all the reactants must beable to withstand the given conditions of time and temperature withoutdecomposition, for example the monocarboxylic and dicarboxylic acidsused must not undergo decarboxylation. The most suitablelactams for thepolycondensation process are aliphatic lactams which contain up to 13ring atoms such as 'y-butyrolactam, fi-valerolactam, e-caprolactam orw-lauryl lactam and the corresponding waminocarboxylic acids such as'y-aminobutyric acid, e-aminocaproic acid or w-aminodecanoic acid.e-Caprolactam is particularly suitable for producing the polyamidesaccording to the invention.

Diethylene triamine, 3,3'-diamino-dipropylamine,

4,4'-diamino-dibutylamine and 6,6-

with each other but diethylene triamine is preferred.

-It has been found that higher valent amines such as triethylenetetramine and tetraethylene pentamine may also be used. fwThedicarboxylicacids used may be aliphatic, aro- :matic or cycloaliphatic,e.g., oxalic acid, succinic acid,

lauric acid,.stearic acid, benzoic acid, benzoic acids substituted withalkyl, halogen or alkoxy groups, or cyclohexane carboxylic acid.Aromatic monocarboxylic acids are particularly suitable, benzoic acidbeing preferred. I

To obtaina basic modified polyamide which can be dyed with reactive dyestoproduce lightfast dyeings which are fastto perspiration, water andboiling detergents even, in deep colour tones, the proportions in whichthe reactants'are used is critical, for example it isessential to add0.1,to 5.0 mol of aliphatic triamine to 100 mol of polycondensablelactam (corresponding to 50 to 440 mval of amino groups per kg in thepolyamide) and preferably 1.0 to 2.0 mol, and to use a quantity ofmonocarboxylic and dicarboxylic acids which correspond to 2 carboxylequivalents to 1 mol of aliphatic triamine. In addition, the molar ratioof monocarboxylic acid to dicarboxylic acid must be between 1 l0 and land is preferably between 3 l and A further object of this invention isthe production of basic modified polyamides produced by thepolycondensation of lactams or cuaminocarboxylic acids with 0.1 to 5 molof triamines of the formula H N(CH ),,Nl-l--(CH ),,NH (where n equals 2to 6) per mol of lactam and 2 equivalents of carboxyl groups in the formof dicarboxylic acids and monocarboxylic acids per mol of triamine,using a molar ratio of monocarboxylic acids to dicarboxylic acids ofbetween 10 l and l 20, which polyamides are dyed with reactive dyes.

The basic modified polyamides produced according to the invention areeminently suitable for the production of threads, films or fibres andhave relative solution viscosities, 1p of between 2.4 and 3.1 andpreferably between 2.6 and 2.8. To achieve the excellent dyeingproperties, it is essential to add aliphatic triamines of the formulashown above in quantities preferably of 1.0 to 2.0 mol per 100 mol ofpolyamide forming lactam. The basic modified polyamides producedaccording to the invention then have amino group contents of betweenmVal/kg and 220 mVal/kg.

The basic modified polyamides produced according to the inventioncontain, per 100 mol of the polyamideforming lactam, 0.1 to 5.0 andpreferably 1.0 to 2.0 recurrent structural units of the general formulaand/or the formula CONH(CH2),,NCO 1 which are capable of reacting withthe reactive groups of reactive dyes to form recurrent structural unitsof the general formula in which n 2 to 6 and X represents the reactivedye radical (reactive dye without the group which is splitted off).

The reactive dyes used for dyeing the polyamides produced according tothe invention and the threads and fibres produced from them arepreferably watersoluble dyes of the azo, anthraquinone or phthalocyanineseries containing 1 to 4 sulpho groups. These dyes must contain at leastone group which is capable of reacting with the fibres. for example themonochlorotriazinyl-, dichlorotriazinyl-, dichloroquinoxalinyl-,trichloropyrimidinyl-, difluoro-chloropyrimidinyl-,methylsulphonyl-benzothiazolyl-, ethylsulphonylbenzothiazolyl,methylsulphonyl-pyrimidinyl-, 4- sulphonamido-benzylchloride-,a-bromoacrylamide-, vinyl sulphoneor B-hydroxyethyl-sulphuric acidsemiester group.

The reactive dye group X is therefore preferably one which correspondsto one of the following formulae D represents a dye group from theseries of azo, anthraquinone or phthalocyanine dyes and represents aphenyl group which may contain sulpho groups.

The dyes used for dyeing the basic modified polyamides are thereforethose corresponding to the following formulae:

Angewandte Chemie 1961, page 125 136;

Angewandte Chemie, 1964, page 423 431;

American Dyestuffs-Reporter 1961, page 505 515;

Dyer 1963, page 891 892; 1964, page 31 37;

SVF-Fachorgan 1964, page 116 123;

Melliand Textilberichte 1967, page 693 696;

lzv. vyssich uc. Zav. Technol. tekstil. Prom. 1966,

page 102 107;

Melliand Textilberichte 1968, 1313 1321;

Melliand'Textilberichte 1968, page 1444 1448;

Kolloidzeitschrift und Zeitschrift Polymere Polymers 1968, Volume 1,page 1 l0;

Textilveredlung 1968, page 241 247;

Textile Chemist and Colorist 1969, page 182 189;

Textil-Praxis 1971, page 241 245;

Textil Research J. 1971, page 518 525;

III

Textil Praxis 1971, page 499 504; German Patent Specifications No.578,742; 578,933;

614,375; 614,896; 650,328; German Offenlegungsschrift No. 1,469,778;

Belgian Patent Specifications No. 563,200; 578,742;

' British Patent Specifications No. 844,869; 844,870;

. 1 SO Na.

S Na. 3

SO2-CH2-CH2OSO3K o 'H II 2 cl C 805E l so H 0 a 0 .5 VII l I l HNH-C\\N/C-HN vIII ao s

NHCO-CHBr-CH Br /L-N N N IX ll 01 N all,

SO Na O Na SO Na Dyeing and printing of the basic modified polyamidesproduced according to the invention is generally carried out by applyingthe dyes to the threads, fibres or start the dyeing process in aslightly acid medium at pH 3 to 5 and then to accelerate and terminatethe reaction between the reactive group of the dye and the amino orimino groups of the polyamide by raising the pH to 7-9 when the bath hasbecome exhausted due to the anionic dye being absorbed by the basicpolyamide salt formation. In the case of printed or pad-dyed textilefabrics or foils, the dyeing process is generally a process ofextraction carried out at 40 to C or of steaming at 100 to 102C.

Under these conditions, the mobile, replaceable Cl, CH -SO and F groupsreferred to as labile groups Z which are attached to the reactive groupsare either split off from the dye molecule and replaced by the amino orimino group of the basic modified polyamides or the addition of anactivated unsaturated carboncarbon bond to the amino or imino group ofthe basic modified polyamides takes place. The linkage between the basicmodified polyamides and the reactive dyes which is obtained by theformation of a covalent bond naturally occurs not only on the modifyingcomponent but also on the normal end groups of the polyamide. The dyedpolyamides obtained in this way preferably contain from 0.1 to 0.5 molof reactive dye for each mol of triamine contained in the basic modifiedpolyamide, which corresponds to 100 mmol of reactive EXAMPLE 1 3575Parts of e-caprolactam, l27 parts of e-aminocaproic acid, 32.5 parts ofdiethylene triamine, 33 parts of adipic acid and 23.5 parts of benzoicacid are heated to 260C for 3 hours under an atmosphere of oxygen freenitrogen without the application of pressure. The

. mixture is then polycondensed by heating for 4 hours most stringentrequirements. Dyed polyamideswhich I,

are consistently superior in the fastness of their colours toperspiration, water and boiling detergents can therefore be obtained inthe brilliant, full colour tones which could previously only be obtainedon cellulose fibres and wool.

Mixtures of cellulose fibres such as cotton or rayon and fibres ofpolyamides produced according to the in vention can be dyed tone-in-tonewith reactive dyes to produce deep colours which are very fast toboiling detergents. In fibres produced from previously known polyamides,on the other hand, the colours obtained by dyeing with reactive dyes arefast to boiling detergents only if they are light in tone and it hastherefore not previously been possible to obtain deep tones fast toboiling detergents on mixtures of polyamide and cellulose fibres.

The high dye fixing capacity of fibres and threads spun from basicmodified polyamides produced according to the invention also makes itpossible to produce multicolour effects by a single bath treatment onmixed fabrics woven or knitted from a mixture of conventional polyamidesand basic modified polyamides produced by the process according to theinvention.

The relative solution viscosities 17 given in the following exampleswere determined in an Ubbelohde viscosimeter at C, using solutions of 10g of substanc in 1 I of m-cresol.

Determination of the amino groups was carried out by potentiometrictitration in a solvent mixture of phenol/chloroform (7:3) against N/lOperchloric acid in glacial acetic acid.

Q r The melting pointswere determined by differential thermoanalysis. qThe sulphurcontent of the dyed' polyamides wasdecally as bariumsulphate. I

"erwise indicated. g I The-following examples are to furtherjllustratethe -inventipnwithoutlirhitingit. 1

usual gravimetri at this temperature with stirring. About 29 parts ofwater are split off, which is equal to the theoretically calculatedquantity. The polycondensate obtained is then spun in water to form abristle (diameter approximately 2.3 to 2.6 mm) which is granulated andfreed from monomeric and oligomeric constituents by boiling withoxygen-free distilled water.

3125 Parts of basic modified polyamide-6 with a relative" solutionviscosity 1 of 2.64 and amino group content of 128 mVal/kg are obtainedafter drying. The polyamide is then spun in a spinning extruder in knownmanner at 280C to form dtex 50 f 9 endless filaments.

l00 Parts of the basic modified polcaprolactam obtained in this way areintroduced into a dyeing apparatus as an endless filament wound on aspool, and a dye bath consisting of 6 parts of the dye of formula I, 0.5parts of triethanolamine dodecylbenzene sulphonate of the followingformula 0 11 O-CH -ZH-OSO 10 parts of anhydrous sodium sulphate, 3 partsof acetic acid and 2000 parts of water is then added at 25 C.

The dye bath was stirred vigorously while heated to 60 C over a periodof 20 minutes and is then heated to C for 20 minutes and finally kept atthis temperature for 60 minutes. The dye bath is then made slightlyalkaline by the addition of 3 parts of anhydrous soda and kept at 100 Cfor 15 minutes. The dye bath is then discharged and a fresh dye bathconsisting of 2000 parts of water and 1 part of Mersolat H is introducedinto the apparatus. The dye bath is kept vigorously circulated whileheated to 100 C for 20 minutes and is then left at this temperature for5 minutes. The dye bath is then discharged and the package on the spoolis dried. A deep red colour which is very fast to washing andperspiration is obtained.

The sulphur content amounts to 0.29 which corresponds to a pure dyestuffcontent of 45.5 mmol per kg of the basic modified polyamide.

If the dyeing process is carried out in the same manner on an ordinarycommercial polycaprolactam endless filament instead of the basicmodified polycaprolactam material, the dye bath is only partly exhaustedand the red colour obtained is comparatively pale and only moderatelyfast to washingand perspiration.

If instead of the basic modified polycaprolactam endless material, equalparts of the polycaprolactam end- Alli-parts and percentages refer toweightgunle ss oth- A less material described in German AuslegeschriftNo. l',223,l00 are used, the dye bath is again substantially exhaustedbut the quantity of dye fixed by the material is'only slightly greaterthan that fixed by the conventional polycaprolactam endless material andthe fastnessto washingand perspiration is therefore-poor. The extractionand fixing of the dye of formula I on to the three various fibrematerials is represented by the extraction curves and fixing curves inFIG. 1 in which A, represents the total quantity of dye extracted byordinary polycaprolactarn which has not been red dyeings which are veryfast to washing and perspiration are again obtained on the basicmodified polycaprolactam endless material. The sulphur content amountsof 0.24 0.33 and 0.28 respectively modifisd with basic groups whichcorresponds to a pure dyestuff content of 25 A represents the quantityof dye which remains fixed mmol, 34-4 mm01 and mmOl/kg 9 the baslc'modl'in ordinary polycaprolactarn not modified with fled p yq If the dyemgProcess 18 agamcav basic groups after it has been treated with soap,ried out in the same manner but the basic modified B, represents thetotal quantity of dye extracted by p y p f @ndless malefrlal 1s replacedy equal polycaprolactam which has been modified by the 10 Parts of lOrdmary Commerclal Polycaprolactam incorporation of tertiayy aminogroups less material, only partly exhausted dye bathsare ob. Brepresents the quantity of dye which remains fixed tamed 9? Case andmparatively pale, light red in polycapmlactam modified by theincorporation dyeings which are only moderately fast to washing and oftertiary amino groups after it has been treated PersP1rat1nwith Soap ifinstead of the basic modlfied polycaprolactam end- C represents thetotal amount of dye extracted by less matenfal equal parts of hpolycaprolactafn polycaprolactam which has bfien modified with lessmaterlal with tertiary ammo groups described in basic groups inaccordance with the invention, German Auslegeschnfl 1121100 are used hC2 represwts the amount of dye which remains fixed dye baths aresubstant ally exhausted but the quant ty in polycaprolactarn modifiedwith basic groups acg ls onlyl i hlgher 3 the j l g cording to theinvention after it has been treated lxed y or nary p0 Ycapro actammatena an Witb p the fastness to washing and persplratlon is thereforeTo obtain these curves, six dyeing processes are carried out side byside, and one is stopped after 10 minutes and the others after 20, 30,40, 70 and 100 minutes EXAMPLES 2 10 respectively. Extinction of the dyeliquor is determined Polycofldensafiong are i d out i a manner i i atthese pomts in time and at the beglnmng f th dye lar to that describedin Example 1 but using the quantimg Process and the exlmctlon Values areCalculated ties shown in Table 1. TAble 2 shows the chemical and percentof the initial extinction of the dye bath at time h i l properties f thebasic modified polyamides I The Prcemages Obtamed are subtraflted fromobtained in these examples. Examples 2 and 5 in which 100 and thedifferences are plotted as extraction values no monocarboxylic id was dare given f in Percent 10, 40, 70 and 100 minutes- 100 parison purposes.The relative viscosities obtained in Parts of the dyeings are removedafter 10 minutes and these examples show that the products obtained areunafter 20, 30, 40, 70 and 100 minutes respectively and suitable forspinning. in each case treated twice with a solution of 2 parts of 100Parts of the basic modified polycaprolactam deanhydrous soda in 2000parts of water at 100C for 15 scribed in Example 7 are introduced in theform of a minutes and the extinction of the combined aftertreatknittedmaterial into a dye vat and a dye liquor consistment liquors isdetermined in each case. ing of5 parts of the dye of formula V, 4 partsof sodium The extinction values obtained in percent of the ini- 4Onaphthalene-1.,3,5,7-tetrasulphonate, 5 parts of anhytial extinction ofthe dye bath at time t 0 are condrous sodium sulphonate, 3 parts ofacetic acid verted to equal dilution ratios and subtracted from the and3000 parts of water is added at 25C. extraction values, and thedifferences are plotted as The liquor is heated to 60C over a period of20 minquantities of dye fixed. utes while the material is kept in motionand it is then instead of the dye of formula 1 equal parts of the 45 atd t C Over a period Of a further 20 minutes dye of formula 11 or offormula ill or TV are used, deep and then kept at this temperature for60 minutes. The

TABLE 1 (Starting materials in mols) Examples 2 3 4 5 6 7 8 9 10e-caprolactan 97 97 97 97 97 97 97 97 97 e-amlnocaprolc acid 3 3 3 3 3 33 3 3 Diethylenetriamine 1 l 1 2 2 2 2 0.5 4 Adipic acid 1 0.8 0.6 2 1.91.7 1.5 0.4 3.7 Benzoic acid 0 0.4 0.8 O 0.2 0.6 1.0 0.2 0.6

Table 2 (Properties of the polyamides) Examples 2 3 4 5 6 7 8 9 l0Melting point C 219 219 218 217 217 217 216 221 212 VISC OSII)' 2m. 3.402.95 2.40 3.30 3.10 2.75 2.42 3.05 2.86 Amino group content mVal/kg 108178 I82 220 75 360 dye bath is'then made slightly alkaline by theaddition of 3 parts of anhydrous soda and kept at. 100C for 15 minutes.The liquor is then discharged and the ,vat filled with fresh liquorconsisting of 3000 parts of water and 1 part of Mersolat H. This isheated to 100C overa period of 20 minutes and then left at thistemperature for 5 minutes while the material is evenly moved through theliquor. The liquor is then discharged and the material dried. A deepblue dyeing which is very fast to washing and perspiration is obtained.The sulphur content amounts to 0.26 which corresponds to a pure dyestuffcontent of 40.4 mmol of the basic modified polyamide.

lf instead of the dye of formula V equal parts of the dye of formula V],or formula VII or VIII are used, the

dyeings obtained on the polycaprolactam produced according to Example 7are again deep blue and very fast to washing and perspiration. Thesulphur content amounts to0.32, 0.39 and 0.27 respectively whichcorresponds to a pure dyestuff content of 49.4 mmol, 40.5 mmol and 43.0mmol per kg of basic modified polyamide.

If the dyeing process is again carried out in the same manner but thebasic modified polycaprolactam endless material described in Example 7is replaced by 5 equal parts of an ordinary commercial polycaprolactamendless material, the dye bath is only partly exhausted and acomparatively pale blue dyeing with only moderate fastness to washingand perspiration is obtained. I

, If instead of the basic modified polycaprolactam endless materialdescribed in Example 7 equal parts of the polycaprolactam endlessmaterial which contains tertiary amino groups described in GermanAuslegeschrift No. 1,223,100 are used, the dye bath is substantiallyexhausted but the dyeing obtained is considerably inferior in itsfastness'to washing and perspiration than that obtained on thepolycaprolactam endless material produced according to Example 7.

Dyeings obtained by reactive dyestuffs using the 40 poly'amides ofExamples 3, 4, 6 and 8 to 10 yield in similar deep dyed polyamides as inExample 7, and they show also good fastness.

EXAMPLE 11 3685 Parts of e-caprolactam, 67.2 parts of diethylenetriamine, 85.6 parts of adipic acid, 15.9 parts of benzoic acid, 12.6parts of TiO and 110.6 parts of water are introduced into a 10 IVA stirrautoclave which has been washed with oxygen-free nitrogen, and thereaction mixture is heated to 260C over a period of 3 hours, duringwhich time a pressure of about 9 atmospheres builds up. When thepolymerisation tempera ture is reached, stirring is continued for onehour under pressure and the pressure is then carefully released from theautoclave over a period of 2 hours. Most of the water introduced withthe reaction mixture distills off in the process. Condensation is thencontinued for 2 hours at thistemperature under a stream of oxygenfreenitrogen and at the same time the water of reaction formed is removed.The total quantity of water obtained is about 150 parts. After one hoursstirring, the polycondensate obtained is spun in the form of a bristleby forcing it into water under a pressure of 5 atmo- 65 spheres ofoxygen-free nitrogen and the bristle is then granulated and extracted.

3635 Parts of basic modified polyamide-6 with a relative solutionviscosity m of 2.59 and an amino group 6 cu 03 Q I (CH2-CH2-0H)3] 2 5parts of anhydrous sodium sulphate, 3 parts of acetic acid and 3000parts of water, and heated to 30C is added.

The liquor is kept in vigorous circulation and at the same time heatedto 60C over a period of 20 minutes and then to C over a period of afurther 20 minutes and then kept at this temperature for 60 minutes. Thedye bath is then made slightly alkaline by the addition of 3 parts ofanhydrous soda and kept at 100C for 15 minutes. The liquor is thendischarged and replaced by a fresh liquor consisting of 3000 parts ofwater and 1 part of Mersolat H.

The fresh liquor is heated to 100C over a period of 20 minutes and thenkept at this temperature for 5 minutes and at the same time vogorouslyagitated. The liquor is then discharged and the yarn dried. A deepyellow colour which is very fast to washing and perspiration isobtained.

The sulphur content of the dyed polyamide amounts to 0.48 whichcorresponds to a pure dyestuff content of 75.0.mmol/kg of the basicmodified polyamide.

If the dye of formula IX is replaced by equal parts of the dye offormula X, a deep yellow colour which is very fast to washing andperspiration is again obtained on the polycaprolactam. The sulphurcontent of the dyed polyamide amounts to 0.42 which corresponds 1 to apure dyestuff content of 66.0 mmol/kg of the basic modified polyamide.If the dyeing process is then again carried out in the same way butusing a commercial polyamide fibre yarn instead of-the fibre yarnproduced from the basic modified polycaprolactam described in Example 1l, the dye bath is only partly exhausted and the yellow colour iscomparatively weak and only moderately fast to washing and perspiration.

If instead of a fiber yarn produced from the basic modifiedpolycaprolactam described in Example 1 1 equal parts of a fibre yarn ofthe polycaprolactam described in German Auslegeschrift No. 1,223,100 areused, the dye bath is substantially exhausted but the colour obtained issubstantially less fast to washing and perspiration than the colourobtained on the polycaprolactam produced according to Example 11.

EXAMPLE l2 1228 Parts of e-caprolactam are polycondensed under pressurewith 1 1.2 parts of diethylene triamine, 17.5 parts of sebacic acid, 5.5parts of cyclohexanecarboxylic acid and 37 parts of water by the methoddescribed in Example 11. The solution viscosity m of j the resultingbasic modified polyamide is 2.89 and the amino group content mVal/kg.

EXAMPLE 13 1228 Parts of c-caprolactam are polycondensed under pressurewith 21.2 parts of 3,3'-diaminodipropylamine, 19 parts of adipic acidand 3.9 parts of acetic acid in the presence of 37 parts of water by themethod described in Example 1 l. The solution viscosity n of theresulting basic modified polyamide is 2.75 and the amino group content157 mVal/kg.

EXAMPLE 14 ter, 100 parts of the printed material is washed in an 20overflow with cold water for 3 minutes, soaped under boiling with 5000parts of a fresh liquor consisting of 2 parts of soda in 998 parts ofwater, for 10 minutes washed with cold water and neutralised with asolution consisting of 2 parts of acetic acid and 998 parts of water.The printed areas of the material are of deep blue colour whereas thenot printed areas remain pure white. The obtained print is fast toboiling washes and perspiration. The sulphur content of the dyedpolyamide amounts to 0.53 which corresponds to a pure dyestuff contentof 82.7 mmol/kg of the basic modified polyamide.

if instead of the basic modified polycaprolactam described in Example 11 an unmodified polycaprolactam is used, only a slight print isobtained.

EXAMPLE 15 10 parts of anhydrous sodium sulphate, 3 parts of 60% aceticacid and 2000 parts of water, is added at 25C.

The liquor is heated to 60C over a period of 20 minutes and at the sametime vigorously agitated, then heated to C over a period of 20 minutesand finally kept at this temperature for 60 minutes. The dye bath isthen made slightly alkaline by the addition of 3 parts of anhydrous sodaand kept at 100C for 15 minutes. The liquor is then discharged and theapparatus filled with a fresh liquor consisting of 2000 parts of waterand l part of Mersolat H. The liquor is vigorously circulated whileheated to 100C over a period of 20 minutes and then kept at thistemperature for 5 minutes. It is then discharged and the granulate isdried. The deep blue granulate obtained is then spun in a spinningextruder in known manner at 240C to form a deep blue endless bristle(diameter approximately 0.1 mm) which is very fast to washing andperspiration.

What we claim is:

1. A process for the production of basic modified polyamides by thepolycondensation of lactams or w-aminocarboxylic acids in the presenceof triamines of the formula HZN 2)" NH M z wherein n equals 2 to 6dicarboxylic acids and monocarboxylic acids, which comprises adding tothe reaction mixture 0.1 to 5.0 mol of the aliphatic triamine per 100mol of the polycondensable lactam and 2 equivalents of carboxyl groupsin the form of dicarboxylic acids and monocarboxylic acids per mol oftriamine and the molar ratio of said monocarboxylic acids to saiddicarboxylic acids being between 10 l and l 20.

2. The process according to claim 1, wherein 1.0 to 2.0 mol of thealiphatic triamine are added.

3. The process according to claim 1, wherein the molar ratio ofmonocarboxylic acids to dicarboxylic acids is between 3 l and l 3.

4. The process according to claim 1, wherein the polycondensable lactamis e-caprolactam.

5. The process according to claim 1, wherein the aliphatic triamine isdiethylene triamine.

6. The process according to claim 1, wherein the monocarboxylic acid anddicarboxylic acid added are benzoic acid and adipic acid.

'7. Basic modified polyamides produced by polycondensation of lactamstogether with 0.1 to 5.0 mol of triamines of the formula 2 2)n NH ah 2wherein n equals to 2 to 6 per 100 mols of lactam and 2 equivalents ofcarboxyl groups in the form of dicarboxylic acids and monocarboxylicacids per mol of triamine, the molar ratio of said monocarboxylic acidsto said dicarboxylic acids being of between 10 1 and 1 20.

3. Threads and fibers consisting of polyamides according to claim 7.

1. A PROCESS FOR THE PRODUCTION OF BASIC MODIFIED POLYAMIDES BY THEPOLYCONDENSATION OF LACTAMS OR W-AMINOCARBOXYLIC ACIDS IN THE PRESENCEOF TRIAMINES OF THE FORMULA
 2. The process according to claim 1, wherein1.0 to 2.0 mol of the aliphatic triamine are added.
 3. The processaccording to claim 1, wherein the molar ratio of monocarboxylic acids todicarboxylic acids is between 3 : 1 and 1 :
 3. 4. The process accordingto claim 1, wherein the polycondeNsable lactam is epsilon -caprolactam.5. The process according to claim 1, wherein the aliphatic triamine isdiethylene triamine.
 6. The process according to claim 1, wherein themonocarboxylic acid and dicarboxylic acid added are benzoic acid andadipic acid.
 7. Basic modified polyamides produced by polycondensationof lactams together with 0.1 to 5.0 mol of triamines of the formulaH2N - (CH2)n- NH - (CH2)n - NH2 wherein n equals to 2 to 6 per 100 molsof lactam and 2 equivalents of carboxyl groups in the form ofdicarboxylic acids and monocarboxylic acids per mol of triamine, themolar ratio of said monocarboxylic acids to said dicarboxylic acidsbeing of between 10 : 1 and 1 :
 20. 8. Threads and fibers consisting ofpolyamides according to claim 7.